Open-shell doublet character in a hexaazatrinaphthylene trianion complex

Moilanen, Jani O.; Day, Benjamin M.; Pugh, Thomas; Layfield, Richard A.

doi:10.1039/c5cc04004c

Cited by 25 publications

(19 citation statements)

References 52 publications

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“…As imilars plit spin density wasr eported for the hexaazatrinaphthylene radicalc omplex. [20] It clearly depicts the coexistence of strong ferromagnetic and antiferromagnetic interactions;t he positive J 1 value is just an apparent value of the spin model in Figure 7d,a nd all of the d-p interactions are antiferromagnetici nF igure 8d as expected. It should be noted that oxidized triphenyleneh as been reported…”

Section: Computational Studies On the Electronic Structures Of The Oxsupporting

confidence: 56%

“…In the three‐electron oxidized species, the spin density in the triphenylene core is split into alpha and beta spins and each part is coupled to d‐spins antiferromagnetically (Figure d). A similar split spin density was reported for the hexaazatrinaphthylene radical complex . It clearly depicts the coexistence of strong ferromagnetic and antiferromagnetic interactions; the positive J 1 value is just an apparent value of the spin model in Figure d, and all of the d–π interactions are antiferromagnetic in Figure d as expected.…”

Section: Resultsmentioning

confidence: 90%

“…It should be noted that such strong interactions could be overestimated due to insufficient treatment of electronic correlations in the B3LYP functional for magnetic calculations . It is also noteworthy that organic open‐shell species might have a multiconfigurational character, and a multireference calculation method such as CASSCF and MRCI could be preferable . In the present study, further investigations into different calculation methods were not performed owing to the lack of experimental values.…”

Section: Resultsmentioning

confidence: 99%

“…[19] It is also noteworthy that organic open-shell species might have am ulticonfigurational character,a nd am ultireference calculation method such as CASSCFa nd MRCI could be preferable. [20] In the presents tudy,f urther investigations into different calculation methods were not performed owing to the lack of experimental values.…”

Section: Computational Studies On the Electronic Structures Of The Oxmentioning

confidence: 99%

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A Trinuclear Iron(III) Complex of a Triple Noninnocent Ligand for Spin‐Structured Molecular Conductors

Hoshino

Akutagawa

2018

Chemistry A European J

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N,N′,N′′,N′′′,N′′′′,N′′′′′‐(Triphenylene‐2,3,6,7,10,11‐hexayl)hexapicolinamide (H6hptp), a triangular ligand containing three noninnocent coordination sites, and its trinuclear iron(III) complex (PPh4)3[FeIII3(hptp)6(CN)6] were prepared. In this complex, three low‐spin Fe3+ ions are coordinated by the triangular hptp6− bridging ligand at its apices. Cyclic voltammetry of (PPh4)3[FeIII3(hptp)6(CN)6] in PhCN solution showed one reductive wave for 3 Fe2+/3 Fe3+ and three oxidative waves for the hptp6− ligand. The controlled‐potential electronic spectra of the solution presented broad absorption bands in the near‐IR (NIR) region for oxidations because a π‐radical is generated on the hptp6− ligand. The EPR spectra of frozen solutions also showed large oxidization‐state dependent differences caused by the strong exchange interactions between the electrons in the d orbitals of the Fe3+ ions and those of the π‐radicals in the hptp6− ligand. The electronic and magnetic states of the oxidized species were investigated using density functional theory.

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Section: Computational Studies On the Electronic Structures Of The Oxsupporting

confidence: 56%

Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Section: Computational Studies On the Electronic Structures Of The Oxmentioning

confidence: 99%

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A Trinuclear Iron(III) Complex of a Triple Noninnocent Ligand for Spin‐Structured Molecular Conductors

Hoshino

Akutagawa

2018

Chemistry A European J

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“…These metrics are consistent with those reported for the only other known complex containing HAN 3−. , (HAN)[Mg(nacnac)] 3 (nacnac= N , N ′‐(2,6‐diisopropylphenyl)‐3,5‐dimethyldiketiminate) …”

Section: Figurementioning

confidence: 97%

A Trinuclear Radical‐Bridged Lanthanide Single‐Molecule Magnet

et al. 2017

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Assembly of the triangular,o rganic radical-bridged complexes Cp* 6 Ln 3 (m 3 -HAN) (Cp* = pentamethylcyclopentadienyl;L n = Gd, Tb,D y; HAN = hexaazatrinaphthylene) proceeds through the reaction of Cp* 2 Ln(BPh 4 )w ith HAN under strongly reducing conditions.S ignificantly,m agnetic susceptibility measurements of these complexes support effective magnetic coupling of all three Ln III centers through the HAN 3À C radical ligand. Thorough investigation of the Dy III congener through both ac susceptibility and dc magnetic relaxation measurements reveals slow relaxation of the magnetization, with an effective thermal relaxation barrier of U eff = 51 cm À1 .M agnetic coupling in the Dy III complex enables al arge remnant magnetization at temperatures up to 3.0 Ki n the magnetic hysteresis measurements and hysteresis loops that are open at zero-field up to 3.5 K.

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Strong Exchange Coupling in a Trimetallic Radical‐Bridged Cobalt(II)‐Hexaazatrinaphthylene Complex

et al. 2016

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Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18‐c‐6 produces [{K(18‐c‐6)}HAN], which contains the S=1/2 radical [HAN].−. The [HAN].− radical can be transferred to the cobalt(II) amide [Co{N(SiMe3)2}2], forming [K(18‐c‐6)][(HAN){Co(N′′)2}3]; magnetic measurements on this compound reveal an S=4 spin system with strong cobalt–ligand antiferromagnetic exchange and J≈−290 cm−1 (−2 J formalism). In contrast, the CoII centres in the unreduced analogue [(HAN){Co(N′′)2}3] are weakly coupled (J≈−4.4 cm−1). The finding that [HAN].− can be synthesized as a stable salt and transferred to cobalt introduces potential new routes to magnetic materials based on strongly coupled, triangular HAN building blocks.

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Open-shell doublet character in a hexaazatrinaphthylene trianion complex

Abstract: Three-electron reduction of hexaazatrinaphthylene with a magnesium(i) reagent gives [(HAN){Mg(nacnac)}3], containing a [HAN]3− ligand with a spin of S = 1/2.

Cited by 25 publications

References 52 publications

A Trinuclear Iron(III) Complex of a Triple Noninnocent Ligand for Spin‐Structured Molecular Conductors

A Trinuclear Iron(III) Complex of a Triple Noninnocent Ligand for Spin‐Structured Molecular Conductors

A Trinuclear Radical‐Bridged Lanthanide Single‐Molecule Magnet

Strong Exchange Coupling in a Trimetallic Radical‐Bridged Cobalt(II)‐Hexaazatrinaphthylene Complex

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